JPWO2020031770A1 - Glow discharge emission analysis method and glow discharge emission analyzer - Google Patents

Abstract

Provided are a glow discharge emission analysis method and a glow discharge emission analyzer that enable effective and rapid pressure adjustment in a glow discharge tube.
In a glow discharge emission analysis method using a glow discharge emission analyzer including a glow discharge tube, a decompression unit for reducing the pressure inside the glow discharge tube, and a gas supply unit for supplying gas to the inside of the glow discharge tube. By arbitrarily designating the upper limit pressure, lower limit pressure, and final pressure and controlling the decompression unit and the gas supply unit, the inside of the glow discharge pipe is depressurized, and between the specified upper limit pressure and lower limit pressure. After increasing or decreasing the pressure inside the glow discharge tube, then adjusting the pressure inside the glow discharge tube to the designated final pressure, adjusting the pressure inside the glow discharge tube to the final pressure, and then Generates glow discharge.

Description

The present invention relates to a glow discharge emission analysis method and a glow discharge emission analyzer.

Conventionally, in order to analyze a component contained in a sample, a glow discharge emission analysis is performed in which the component is analyzed using a glow discharge. The glow discharge tube for generating a glow discharge includes an electrode having a cylindrical portion. The sample to be analyzed is arranged so as to face the cylindrical portion, a gas such as an inert gas is supplied into the glow discharge tube, and a voltage is applied between the cylindrical portion of the electrode and the sample to generate a glow discharge. do. The surface of the sample is sputtered by the plasma generated by the glow discharge, and particles such as atoms or molecules emitted from the sample by the sputtering are excited to emit light. The component analysis of the sample is performed by spectroscopically generating the generated light.

After the glow discharge, the substance released from the sample by sputtering adheres to the electrode. The electrodes need to be cleaned before the next sample analysis. In cleaning, substances adhering to the electrodes are removed using a cleaning tool such as a brush. At this time, substances such as hydrocarbons existing in the atmosphere may adhere to the electrodes. The generation of plasma becomes unstable due to the substance attached to the electrode, and the substance attached to the electrode may be detected as a component of the sample.

Therefore, a technique has been developed in which an electrode is coated with a substance emitted from a simulated sample by performing a glow discharge using a simulated sample whose components are known before performing glow discharge emission analysis of the sample. After the glow discharge using the simulated sample, the glow discharge emission analysis using the sample is performed. By coating the electrodes, the generation of plasma is stabilized and the influence on the component analysis of the sample is reduced. Patent Document 1 discloses a technique using a gold plate as a simulated sample.

Japanese Unexamined Patent Publication No. 2001-91465

In order to perform glow discharge emission analysis on a plurality of samples, cleaning of the electrodes, glow discharge using simulated samples, and analysis of the samples are repeated. When cleaning the electrodes and when exchanging the simulated sample with a sample for analysis, it is necessary to set the pressure in the glow discharge tube to atmospheric pressure. Further, at the time of glow discharge using a simulated sample and analysis of the sample, the inside of the glow discharge tube is depressurized and gas is supplied into the glow discharge tube. In order to analyze a plurality of samples, it is necessary to repeatedly adjust the pressure in the glow discharge tube by reducing the pressure and supplying gas. Therefore, it is desirable to adjust the pressure quickly.

If the atmosphere remains in the glow discharge tube during the glow discharge emission analysis, the plasma generation becomes unstable and the component analysis of the sample is adversely affected. Therefore, pumping may be performed to push out the atmosphere with the supplied inert gas. However, when the pumping is performed without darkness, the consumption of the inert gas becomes large, and the time required for adjusting the pressure in the glow discharge tube becomes long.

The present invention has been made in view of such circumstances, and an object of the present invention is a glow discharge emission analysis method and a glow that enable effective and rapid pressure adjustment in a glow discharge tube. The purpose is to provide a discharge emission analyzer.

The glow discharge emission analysis method according to the present invention includes a glow discharge tube, a pressure reducing section for reducing the pressure inside the glow discharge tube, and a gas supply section for supplying gas to the inside of the glow discharge tube. In the glow discharge emission analysis method using the apparatus, the inside of the glow discharge tube is depressurized by arbitrarily designating the upper limit pressure, the lower limit pressure, and the final pressure and controlling the decompression unit and the gas supply unit. The pressure inside the glow discharge tube is increased or decreased between the specified upper limit pressure and the lower limit pressure, and then the pressure inside the glow discharge tube is adjusted to the specified final pressure, and the inside of the glow discharge tube is adjusted. After adjusting the pressure of the above to the final pressure, a glow discharge is generated.

In the present invention, the upper limit pressure, the lower limit pressure, and the final pressure for adjusting the pressure in the glow discharge tube by depressurizing and supplying gas are arbitrarily specified. In pressure adjustment, the pressure in the glow discharge tube is reduced, the pressure is increased or decreased between the upper limit pressure and the lower limit pressure, and the pressure is adjusted to the final pressure. After adjusting the pressure, a glow discharge is generated. By arbitrarily specifying the upper limit pressure, the lower limit pressure, and the final pressure, the pumping conditions performed at the time of pressure adjustment can be adjusted. By adjusting the pumping conditions, it becomes possible to perform pumping under appropriate conditions.

In the glow discharge emission analysis method according to the present invention, the number of times the pressure inside the glow discharge tube is increased or decreased is arbitrarily specified, and the pressure inside the glow discharge tube is repeatedly increased or decreased by the specified number of times. It is a feature.

In the present invention, the number of times the pressure in the glow discharge tube is increased or decreased between the upper limit pressure and the lower limit pressure is arbitrarily specified. By specifying the number of times the pressure is increased or decreased, the pumping conditions can be adjusted in more detail.

In the glow discharge emission analysis method according to the present invention, the first time to be applied to increase the pressure inside the glow discharge tube from the lower limit pressure to the upper limit pressure, and the pressure inside the glow discharge tube are set to the upper limit. The second time to be applied to reduce the pressure from the pressure to the lower limit pressure is arbitrarily specified, the pressure inside the glow discharge tube is reduced to the lower limit pressure, and the glow discharge tube is reduced to the designated first time. It is characterized by increasing the pressure inside the glow discharge tube and decreasing the pressure inside the glow discharge tube for a designated second time.

In the present invention, the first time to be applied to increase the pressure in the glow discharge tube from the lower limit pressure to the upper limit pressure and the second time to be applied to decrease the pressure from the upper limit pressure to the lower limit pressure are arbitrarily specified. do. By specifying the time required for the pressure to increase and decrease, the pumping conditions can be adjusted in more detail.

In the glow discharge emission analysis method according to the present invention, the glow discharge tube has an electrode, and the electrode and the simulated sample are arranged in a state where a simulated sample having the same components as the electrode is arranged facing the electrode. Glow discharge is generated between the electrodes, the simulated sample is removed, the sample is placed so as to face the electrode, glow discharge is generated between the electrode and the sample, and glow discharge emission analysis is performed. It is characterized by.

In the present invention, the electrode is coated with a constituent material of the simulated sample by generating a glow discharge in a state where a simulated sample having the same components as the electrode of the glow discharge tube is opposed to the electrode. Then, the glow discharge emission analysis is performed with the sample to be analyzed facing the electrode. Even if substances such as hydrocarbons existing in the atmosphere adhere to the electrodes during cleaning, the coating makes it difficult for the adhered substances to be released. Therefore, it is suppressed that the attached substance affects the glow discharge emission analysis.

In the glow discharge emission analysis method according to the present invention, the simulated sample and the sample moving unit that holds and holds the simulated sample and the sample are used, and the simulated sample is transferred to the electrode by the sample moving unit. After generating a glow discharge between the electrode and the simulated sample, the simulated sample was removed from the position by the sample moving unit, and the sample was opposed to the electrode. It is characterized by being placed in a position.

In the present invention, the sample moving unit arranges and removes the simulated sample and arranges the sample. Placement and removal of the simulated sample and placement of the sample are performed automatically. When performing glow discharge emission analysis of a plurality of samples, the plurality of samples are sequentially arranged.

In the glow discharge emission analysis method according to the present invention, the glow discharge tube is provided by the gas supply unit when the simulated sample is arranged to face the electrode and when the sample is arranged to face the electrode. It is characterized by changing the type of gas supplied to the inside of the.

In the present invention, the type of gas supplied to the inside of the glow discharge tube is changed between when a simulated sample is made to face an electrode to generate a glow discharge and when a glow discharge emission analysis of the sample is performed. By changing the type of gas, it is possible to carry out the generation of glow discharge using a simulated sample and the analysis of glow discharge emission of the sample under appropriate conditions.

The glow discharge emission analyzer according to the present invention includes a glow discharge tube, a pressure reducing unit for reducing the pressure inside the glow discharge tube, a gas supply unit for supplying gas to the inside of the glow discharge tube, and a control unit. In the glow discharge emission analyzer, the control unit accepts the designation of the upper limit pressure, the lower limit pressure, and the final pressure at arbitrary values, and controls the decompression unit and the gas supply unit to obtain the specified upper limit pressure and the specified upper limit pressure. The pressure inside the glow discharge tube is increased or decreased between the lower limit pressures, then the pressure inside the glow discharge tube is adjusted to the specified final pressure, and the pressure inside the glow discharge tube is adjusted to the final pressure. It is characterized in that a glow discharge is generated after adjusting to.

In the present invention, the glow discharge emission analyzer accepts the designation of the upper limit pressure, the lower limit pressure, and the final pressure for adjusting the pressure in the glow discharge tube at arbitrary values. In the pressure adjustment, the glow discharge emission analyzer reduces the pressure in the glow discharge tube, increases or decreases the pressure between the upper limit pressure and the lower limit pressure, and adjusts the pressure to the final pressure. By arbitrarily specifying the upper limit pressure, the lower limit pressure, and the final pressure, the pumping conditions performed at the time of pressure adjustment can be adjusted. By adjusting the pumping conditions, the glow discharge emission analyzer can perform pumping under appropriate conditions.

In the glow discharge emission analyzer according to the present invention, the glow discharge tube has an electrode, holds a simulated sample and a sample having the same components as the electrode, and moves the held simulated sample and the sample. A moving unit is further provided, the sample moving unit arranges the simulated sample at a position facing the electrode, and the control unit arranges the simulated sample at the position, and the electrode and the simulated sample A glow discharge was generated between the samples, the sample moving unit removed the simulated sample from the position, the sample was placed at a position facing the electrode, and the control unit placed the sample at the position. In this state, a glow discharge is generated between the electrode and the sample, and glow discharge emission analysis is performed.

In the present invention, a glow discharge is generated in a state where a simulated sample having the same composition as the electrode of the glow discharge tube is opposed to the electrode, and then a glow discharge emission analysis is performed in a state where the sample to be analyzed is opposed to the electrode. I do. The electrodes are coated with the constituent substances of the simulated sample, making it difficult for the substances adhering to the electrodes to be released during cleaning. In addition, the sample moving unit arranges and removes the simulated sample and arranges the sample. Placement and removal of the simulated sample and placement of the sample are performed automatically.

In the present invention, it is possible to perform pumping under appropriate conditions, and it is possible to effectively and quickly adjust the pressure in the glow discharge, which is an excellent effect.

It is a block diagram which shows the structure of the glow discharge emission analyzer which concerns on Embodiment 1. FIG. It is sectional drawing which shows the example of the internal structure of a glow discharge tube. It is a block diagram which shows the structural example of a control part. It is a conceptual diagram which shows the outline of the glow discharge emission analysis method. It is a block diagram which shows the example of the structure of the gas supply part. It is a flowchart which shows the procedure of the process which the control part executes for the glow discharge emission analysis. It is a schematic diagram which shows the example of the reception screen for accepting the specification of a parameter. It is a graph which shows the example of pressure adjustment schematically. It is a graph which shows the example of the result of the glow discharge emission analysis. It is a graph which shows the example of the result of the glow discharge emission analysis. It is a block diagram which shows the structure of the glow discharge emission analyzer 10 which concerns on Embodiment 2. It is a schematic perspective view which shows the sample plate. It is sectional drawing which shows the arrangement example of the sample plate and the glow discharge tube which concerns on Embodiment 2 when a glow discharge is performed. It is a flowchart which shows the procedure of the process which concerns on Embodiment 2 that the control part executes for the glow discharge emission analysis. It is a schematic diagram which shows the positional relationship of the glow discharge tube, the sample plate and the cleaning tool which concerns on Embodiment 2 at the time of cleaning. It is a schematic diagram which shows the positional relationship of the glow discharge tube, the sample plate and the cleaning tool which concerns on Embodiment 2 when performing a glow discharge using a simulated sample. It is a schematic diagram which shows the positional relationship of the glow discharge tube, the sample plate and the cleaning tool which concerns on Embodiment 2 when performing a glow discharge emission analysis.

Hereinafter, the present invention will be specifically described with reference to the drawings showing the embodiments thereof.
<Embodiment 1>
FIG. 1 is a block diagram showing a configuration of a glow discharge emission analyzer 10 according to the first embodiment. The glow discharge emission analyzer 10 includes a glow discharge tube 1, a spectroscopic measuring instrument 41, a power supply unit 42, and a control unit 2. The glow discharge tube 1 generates a glow discharge. The spectroscopic measuring instrument 41 disperses the light generated by the glow discharge and measures the intensity of the light. The power supply unit 42 generates a high frequency voltage for generating a glow discharge. The control unit 2 controls the glow discharge emission analyzer 10 as a whole. The sample 51 to be analyzed is arranged by pressing it against the glow discharge tube 1 with the pressing electrode 43. The pressing electrode 43 is formed in a block shape and is connected to the power supply unit 42.

The glow discharge emission analyzer 10 further includes a decompression unit 44, a gas supply unit 3, and a pressure sensor 45. The decompression unit 44 decompresses the inside of the glow discharge tube 1. The decompression unit 44 includes, for example, a vacuum pump. A pipe for reducing pressure is arranged between the pressure reducing unit 44 and the glow discharge pipe 1. The gas supply unit 3 supplies a gas containing an inert gas to the inside of the glow discharge pipe 1. The gas supply unit 3 includes a cylinder filled with gas. A pipe for supplying gas is arranged from the gas supply unit 3 to the glow discharge pipe 1. The pressure sensor 45 measures the pressure inside the glow discharge tube 1. The spectroscopic measuring instrument 41, the power supply unit 42, the decompression unit 44, the gas supply unit 3, and the pressure sensor 45 are connected to the control unit 2. The control unit 2 controls the operations of the spectroscopic measuring instrument 41, the power supply unit 42, the decompression unit 44, and the gas supply unit 3.

FIG. 2 is a cross-sectional view showing an example of the internal configuration of the glow discharge tube 1. The glow discharge tube 1 is composed of a short columnar lamp body 11, an anode 12, a ceramic member 13, and a pressing block 15. The anode 12 corresponds to the electrode.

The lamp body 11 is provided with a recess 11b for attaching the anode 12 at the center of the end surface 11a to which the pressing block 15 is combined. A central hole 11c is formed in the center of the recess 11b. The lamp body 11 is provided with a plurality of suction holes 11e and 11f for reducing pressure from the peripheral wall portion 11d toward the center. Some suction holes 11e communicate with the central hole 11c, and other suction holes 11f communicate with the recess 11b side. A pipe connected to the decompression unit 44 is connected to the suction holes 11e and 11f. Further, the lamp body 11 is formed so that the gas supply hole 11g for gas supply communicates with the center hole 11c from the peripheral wall portion 11d toward the center. A pipe connected to the gas supply unit 3 is connected to the gas supply hole 11g. Further, the lamp body 11 has a ground potential connected to the ground wire.

The anode 12 housed in the recess 11b of the lamp body 11 has a shape in which the cylindrical portion 12b protrudes from the center of the disk portion 12a. A through hole 12c penetrating the disk portion 12a is bored from the inside of the cylindrical portion 12b. Further, a hole 12d is also formed in the disk portion 12a. When the anode 12 is attached to the recess 11b of the lamp body 11, the central hole 11c and the through hole 12c of the lamp body 11 communicate with each other substantially coaxially. When the anode 12 is attached to the recess 11b of the lamp body 11, it reaches the ground potential via the lamp body 11. Further, when the anode 12 is attached to the lamp body 11, the cylindrical portion 12b is in a state of protruding from the end surface 11a of the lamp body 11. An O-ring is attached between the lamp body 11 and the anode 12 in order to maintain the airtightness of the central hole 11c of the lamp body 11 and the through hole 12c of the anode 12 in the state where the anode 12 is housed.

A window 16 for transmitting light is provided at an end of the central hole 11c of the lamp body 11 opposite to the end communicating with the through hole 12c of the anode 12. A spectroscopic measuring instrument 41 is connected to the outside of the window 16. The spectroscopic measuring instrument 41 disperses the light transmitted through the window 16 and incident into the spectroscopic measuring instrument 41 using a diffraction grating or the like, and measures the intensity of the dispersed light of each wavelength by using a photoelectron multiplying tube or the like. .. The operation of the spectroscopic measuring instrument 41 is controlled by the control unit 2, and the measurement result is input to the control unit 2.

The ceramic member 13 arranged so as to cover the anode 12 is made of an insulating ceramic. The ceramic member 13 is formed in a thick disk shape, and has a flange portion 13d that covers the disk portion 12a of the anode 12. An insertion hole 13c through which the cylindrical portion 12b of the anode 12 is inserted is formed at a central portion of the ceramic member 13. The ceramic member 13 is arranged so as to face the disk portion 12a of the anode 12, and an O-ring is attached between the ceramic member 13 and the disk portion 12a to maintain airtightness. In the state where the ceramic member 13 is arranged, a predetermined gap is formed between the insertion hole 13c and the cylindrical portion 12b of the anode 12.

The pressing block 15 for fixing the anode 12 and the ceramic member 13 to the lamp body 11 is a member formed of an insulating material in an annular shape. The pressing block 15 presses the flange portion 13d of the ceramic member 13 toward the lamp body 11 by the protruding portion 15a on the inner peripheral edge side. The pressing block 15 itself is attached to the end surface 11a of the lamp body 11 by bolts. The pressing block 15 is attached so as to project from the end surface 11a of the lamp body 11, and the ceramic member 13 and the cylindrical portion 12b of the anode 12 are arranged inside the pressing block 15. An insertion hole 13c is opened in the end surface 13a of the ceramic member 13, and a cylindrical portion 12b of the anode 12 is arranged in the insertion hole 13c. The opening end of the insertion hole 13c is the opening 13b of the glow discharge tube 1, and the opening 13b is located at a position facing the tip 12e of the cylindrical portion 12b.

An O-ring 17 surrounding the opening 13b is arranged on the end surface 13a of the ceramic member 13. The sample 51 is arranged so that the surface abuts on the O-ring 17. For example, the sample 51 has a flat plate shape. The outer shape of the sample 51 is a size that exceeds the outer diameter of the O-ring 17. A pressing electrode 43 is pressed against the back side of the sample 51, and the sample 51 is pressed against the glow discharge tube 1. The pressing electrode 43 presses the sample 51 against the glow discharge tube 1 by a predetermined locking means (not shown). In this way, the sample 51 is arranged so as to close the opening 13b, and the surface of the sample 51 faces the tip 12e of the cylindrical portion 12b of the anode 12.

With the sample 51 arranged so as to close the opening 13b, the inside of the glow discharge tube 1 is depressurized by the decompression unit 44. The sample 51 is fixed by the decompression unit 44 depressurizing the inside of the glow discharge tube 1. The gas supply unit 3 supplies gas to the inside of the glow discharge pipe 1. The gas supplied is a gas that enables the generation of glow discharge, such as argon gas. The power supply unit 42 supplies a high frequency voltage to the pressing electrode 43. By supplying a high frequency voltage to the pressing electrode 43, a voltage is applied between the anode 12 and the sample 51.

Gas is supplied to the space between the tip 12e of the cylindrical portion 12b of the anode 12 and the sample 51 at any time, and a voltage is applied between the anode 12 and the sample 51 to form a voltage between the anode 12 and the sample 51. Glow discharge occurs. When glow discharge occurs, plasma containing gas ions is generated. The gas ions are accelerated in the through hole 12c by the voltage, collide with the surface of the sample 51 facing the tip 12e of the cylindrical portion 12b, and sputtering is performed. By sputtering, the constituent substances of the sample 51 are released as particles. The emitted particles are excited by glow discharge and emit light having a wavelength peculiar to the element contained in the particles. The emitted light passes through the window 16 and is incident on the spectroscopic measuring instrument 41. The spectroscopic measuring instrument 41 disperses the incident light, measures the intensity of the light of each wavelength, and inputs the measurement result to the control unit 2. .. The control unit 2 performs a qualitative analysis or a quantitative analysis of the components contained in the sample 51 based on the measurement result input from the spectroscopic measuring device 41. In this way, the glow discharge emission analysis for the sample 51 is performed.

FIG. 3 is a block diagram showing a configuration example of the control unit 2. The control unit 2 is configured by using a computer such as a personal computer. The control unit 2 includes a CPU (Central Processing Unit) 21 for performing calculations, a RAM (Random Access Memory) 22, a drive unit 23, an input unit 24, a storage unit 25, and a display unit 26. The RAM 22 stores temporary information generated by the calculation. The drive unit 23 reads information from a recording medium 20 such as an optical disc. The input unit 24 inputs information such as various processing instructions operated by the user. For example, the input unit 24 is a keyboard or a pointing device. The storage unit 25 is non-volatile, and includes, for example, a hard disk or a non-volatile memory. The display unit 26 displays various types of information. For example, the display unit 26 is a liquid crystal display.

The CPU 21 causes the drive unit 23 to read the computer program 251 from the recording medium 20, and stores the read computer program 251 in the storage unit 25. The CPU 21 loads the computer program 251 from the storage unit 25 into the RAM 22 as needed, and executes the necessary processing in the control unit 2 according to the loaded computer program 251. The control unit 2 does not have to include the drive unit 23. The computer program 251 may be downloaded from an external server device (not shown) to the control unit 2 and stored in the storage unit 25. Further, the control unit 2 may be in a form in which a recording medium on which the computer program 251 is recorded is provided inside, instead of accepting the computer program 251 from the outside.

The control unit 2 further includes an interface unit 27. A spectroscopic measuring instrument 41, a power supply unit 42, a decompression unit 44, a gas supply unit 3, and a pressure sensor 45 are connected to the interface unit 27. The CPU 21 performs a process for controlling the operations of the spectroscopic measuring instrument 41, the power supply unit 42, the decompression unit 44, and the gas supply unit 3 through the interface unit 27. The control unit 2 receives the measurement result input from the spectroscopic measuring device 41 at the interface unit 27. The pressure sensor 45 inputs the information indicating the measured pressure to the control unit 2, and the control unit 2 receives the information indicating the pressure at the interface unit 27.

The glow discharge emission analysis method according to this embodiment will be described. FIG. 4 is a conceptual diagram showing an outline of the glow discharge emission analysis method. First, the anode 12 of the glow discharge tube 1 is cleaned using a cleaning tool 52 such as a brush. By cleaning, the substance adhering to the inner surface of the through hole 12c of the anode 12 is removed. After performing the glow discharge emission analysis, since the substances released from the sample 51 are attached to the inner surface of the through hole 12c, these substances are removed. When the glow discharge is generated after this, the generation of plasma is stabilized, and the influence of the substance contained in the previously analyzed sample 51 on the result of the subsequent analysis is reduced.

Next, a simulated sample 53 different from the sample 51 to be analyzed is attached to the glow discharge tube 1 to generate a glow discharge. The simulated sample 53 is composed of the same components as the anode 12. For example, the anode 12 and the simulated sample 53 are made of copper. The simulated sample 53 is not the subject of component analysis. The simulated sample 53 is arranged so as to close the opening 13b, similarly to the sample 51 shown in FIG. The surface of the simulated sample 53 faces the tip 12e of the cylindrical portion 12b. With the simulated sample 53 arranged, the decompression section 44 decompresses the inside of the glow discharge tube 1, and the gas supply section 3 supplies gas to the inside of the glow discharge tube 1. At this time, by adjusting the pressure in the glow discharge tube 1, pumping is performed to push out the atmosphere in the glow discharge tube 1 with a gas. The power supply unit 42 supplies a high frequency voltage to the pressing electrode 43, and a glow discharge is generated between the anode 12 and the simulated sample 53.

When the glow discharge occurs, sputtering is performed on the simulated sample 53. By sputtering, the constituent substances of the simulated sample 53 are ejected as particles. The ejected particles adhere to the inner surface of the through hole 12c of the anode 12. Therefore, the inner surface of the through hole 12c is coated with the constituent material of the simulated sample 53. The spectrophotometer 41 does not have to measure light. During the above-mentioned cleaning, substances such as hydrocarbons existing in the atmosphere adhere to the inner surface of the through hole 12c of the anode 12. The coating is performed on the substance adhering to the inner surface of the through hole 12c. Therefore, after that, the substance adhering to the inner surface of the through hole 12c is difficult to be released.

Next, the pressure inside the glow discharge tube 1 is returned to atmospheric pressure, and the simulated sample 53 is removed from the glow discharge tube 1. Further, the sample 51 to be analyzed is attached to the glow discharge tube 1 without cleaning. By not cleaning, substances in the atmosphere are prevented from further adhering to the inner surface of the through hole 12c of the anode 12. With the sample 51 arranged so as to close the opening 13b, the decompression section 44 decompresses the inside of the glow discharge tube 1, and the gas supply section 3 supplies gas to the inside of the glow discharge tube 1. At this time, pumping is performed. A glow discharge is generated between the anode 12 and the sample 51, and a glow discharge emission analysis for the sample 51 is performed.

Since the substance adhered to the inner surface of the through hole 12c is difficult to be released due to the coating, the generation of plasma is stable during the glow discharge emission analysis. It is unlikely that the substance adhering to the inner surface of the through hole 12c will be released, excited and emit light, and that this light will be measured by the spectrophotometer 41. Therefore, it is unlikely that the substance adhering to the inner surface of the through hole 12c will be detected as a component of the sample 51 by the glow discharge emission analysis. The constituent material of the simulated sample 53 coated on the inner surface of the through hole 12c can be released from the inner surface of the through hole 12c during the glow discharge emission analysis. Since the constituent substance of the simulated sample 53 is the same as the constituent substance of the anode 12, the influence of the constituent substance of the simulated sample 53 on the component analysis of the sample 51 is the same as the influence of the constituent substance of the anode 12. That is, the substance coating the inner surface of the through hole 12c does not increase the influence on the component analysis of the sample 51.

After the glow discharge emission analysis for the sample 51 is performed, the pressure inside the glow discharge tube 1 is returned to atmospheric pressure, and the anode 12 is cleaned. By repeating cleaning of the anode 12, glow discharge using the simulated sample 53, and analysis of the sample 51, glow discharge emission analysis for a plurality of samples 51 is performed. Cleaning using the cleaning tool 52 and attachment / detachment of the simulated sample 53 and the sample 51 to the glow discharge tube 1 are performed manually.

In the present embodiment, the type of gas supplied from the gas supply unit 3 can be changed between when performing glow discharge using the simulated sample 53 and when performing glow discharge emission analysis of the sample 51. FIG. 5 is a block diagram showing an example of the configuration of the gas supply unit 3. The gas supply unit 3 includes a first cylinder 31 filled with gas for performing glow discharge using the simulated sample 53 and a second cylinder filled with gas for performing glow discharge emission analysis of the sample 51. It has 32 and. A solenoid valve 311 is connected to the first cylinder 31, and a solenoid valve 321 is connected to the second cylinder 32. The solenoid valves 311 and 321 are arranged in a pipe 30 for supplying gas to the glow discharge pipe 1. The solenoid valves 311 and 321 are connected to the control unit 2, and the operation is controlled by the control unit 2. With the solenoid valve 311 open and the solenoid valve 321 closed, the gas filled in the first cylinder 31 is supplied to the inside of the glow discharge pipe 1 through the solenoid valve 311 and the pipe 30. Further, in a state where the solenoid valve 321 is opened and the solenoid valve 311 is closed, the gas filled in the second cylinder 32 is supplied to the inside of the glow discharge pipe 1 through the solenoid valve 321 and the pipe 30.

In general, the gas suitable for performing glow discharge using the simulated sample 53 is different from the gas suitable for performing glow discharge emission analysis of sample 51. In order to perform glow discharge using the simulated sample 53, the gas used may be any gas that easily causes sputtering. For example, the gas for performing glow discharge using the simulated sample 53 is argon gas. The first cylinder 31 is filled with argon gas. The gas for performing glow discharge using the simulated sample 53 may be neon gas. In this case, the first cylinder 31 is filled with neon gas.

In order to perform glow discharge emission analysis of the sample 51, it is desirable that the gas used is a gas in which gas ions can excavate the sample 51 at an appropriate rate by sputtering. When the excavation rate is low, the amount of substance released from the sample 51 by sputtering is small, the emission intensity is low, and the accuracy of analysis is low. When the sample 51 is composed of a substance containing carbon, it is desirable that the gas used contains oxygen. For example, when the sample 51 is DLC (Diamond-like Carbon), the gas used for the glow discharge emission analysis is a mixed gas of argon gas and oxygen gas. The second cylinder 32 is filled with a mixed gas of argon gas and oxygen gas. Further, for example, when the sample 51 contains a trace amount of fluorine of 1% or less in the DLC, the gas used is neon gas. The second cylinder 32 is filled with pure neon gas. Further, for example, when the sample 51 contains a trace amount of fluorine of several% or more in the DLC, the gas used is a mixed gas of neon gas and oxygen gas. The second cylinder 32 is filled with a mixed gas of neon gas and oxygen gas.

If the type of gas can be changed between the glow discharge using the simulated sample 53 and the glow discharge emission analysis of the sample 51, an appropriate gas can be selected. By selecting an appropriate gas, the glow discharge using the simulated sample 53 and the glow discharge emission analysis of the sample 51 can be performed under appropriate conditions, respectively. Therefore, glow discharge is stably generated. Further, when a gas capable of excavating the sample 51 at an appropriate rate is used, an appropriate amount of a substance is released from the sample 51 by sputtering, the emission intensity is improved, and accurate glow discharge emission analysis is performed. It becomes possible.

FIG. 6 is a flowchart showing a procedure of processing executed by the control unit 2 for the glow discharge emission analysis according to the first embodiment. Hereinafter, the step is abbreviated as S. The CPU 21 of the control unit 2 executes the following processing according to the computer program 251. At the stage where the anode 12 of the glow discharge tube 1 is cleaned, the CPU 21 performs a process of accepting the designation of the parameter for adjusting the pressure inside the glow discharge tube 1 (S1). In S1, the CPU 21 displays a reception screen for accepting the parameter designation on the display unit 26, and receives the parameter input on the input unit 24 by the operation of the user.

FIG. 7 is a schematic diagram showing an example of a reception screen for accepting parameter designations. In the pressure adjustment according to the present embodiment, the pressure in the glow discharge tube 1 is increased or decreased a plurality of times. The reception screen includes an input field for inputting the number of times the pressure is increased or decreased repeatedly. The user operates the input unit 24 to specify the number of repetitions numerically, and the CPU 21 accepts the designation of the number of repetitions. The reception screen further includes an input field for inputting the lower limit pressure and the upper limit pressure for increasing or decreasing the pressure, and the final pressure to be finally adjusted. The user operates the input unit 24 to specify the lower limit pressure, the upper limit pressure, and the final pressure numerically, and the CPU 21 accepts the designation of the lower limit pressure, the upper limit pressure, and the final pressure.

The reception screen shows the first time, which is the time to be applied to increase the pressure in the glow discharge tube 1 from the lower limit pressure to the upper limit pressure, and the time to be applied to decrease the pressure from the upper limit pressure to the lower limit pressure. An input field for entering the second time is further included. The reception screen further includes an input field for inputting a third time, which is the time to be applied from the completion of increasing or decreasing the pressure to the final pressure. The user operates the input unit 24 to specify the first time, the second time, and the third time numerically, and the CPU 21 accepts the designation of the first time, the second time, and the third time.

In S1, the user can arbitrarily specify parameters including the number of repetitions, the lower limit pressure, the upper limit pressure, the final pressure, the first time, the second time, and the third time, and the CPU 21 arbitrarily specifies the parameters. Accept numerically. These parameters are arbitrarily specified by S1. The final pressure needs to be specified as the pressure at which glow discharge can occur. The CPU 21 stores the designated parameter in the storage unit 25. In S1, the CPU 21 may read the parameters stored in the storage unit 25 and display the reception screen including the values of the read parameters on the display unit 26. Further, the CPU 21 may randomly generate parameter values and display a reception screen including the generated parameter values on the display unit 26. The treatment of S1 may be performed in parallel with the cleaning of the anode 12, or may be performed in advance of the cleaning of the anode 12.

Next, the CPU 21 selects the gas for the simulated sample 53 as the gas to be supplied to the inside of the glow discharge tube 1 (S2). That is, the CPU 21 selects a gas for performing glow discharge using the simulated sample 53. In this embodiment, the CPU 21 selects a gas (for example, argon gas) filled in the first cylinder 31. The type of gas for the simulated sample 53 is set in advance, and setting information indicating the type of gas is stored in the storage unit 25 in advance. In S2, the control unit 2 may receive the gas designation at the input unit 24 and perform a process of selecting the designated gas.

The CPU 21 adjusts the pressure inside the glow discharge tube 1 in a state where the simulated sample 53 is arranged so as to close the opening 13b (S3). The CPU 21 controls the decompression unit 44 and the gas supply unit 3 based on the pressure value measured by the pressure sensor 45. More specifically, the CPU 21 controls the operation of the decompression unit 44, and adjusts the amount of gas discharged from the glow discharge tube 1 by the decompression unit 44. Further, the CPU 21 closes the solenoid valve 321 and controls the degree of opening of the solenoid valve 311 to adjust the amount of gas flowing from the first cylinder 31 through the pipe 30 into the glow discharge pipe 1.

FIG. 8 is a graph schematically showing an example of pressure adjustment. The horizontal axis of FIG. 8 shows the elapsed time, and the vertical axis shows the pressure in the glow discharge tube 1. At the time when the pressure adjustment is started, the pressure in the glow discharge tube 1 is substantially the same as the atmospheric pressure. The pressure inside the glow discharge pipe 1 is reduced by the CPU 21 operating the pressure reducing unit 44 and the pressure reducing unit 44 depressurizing the inside of the glow discharge pipe 1. The CPU 21 controls the decompression unit 44 so that the pressure is reduced to a designated lower limit pressure based on the pressure value measured by the pressure sensor 45. Next, the CPU 21 controls the gas supply unit 3, and the gas supply unit 3 supplies gas to the inside of the glow discharge pipe 1, so that the pressure in the glow discharge pipe 1 increases.

The CPU 21 controls the gas supply unit 3 so that the increase in pressure stops at a designated upper limit pressure based on the value of the pressure measured by the pressure sensor 45. At this time, the CPU 21 increases the pressure in the glow discharge tube 1 for the first hour from the time when the pressure in the glow discharge tube 1 reaches the lower limit, and the pressure reaches the upper limit when the first time elapses. The pressure reducing unit 44 and the gas supply unit 3 are controlled so as to obtain pressure.

The CPU 21 then reduces the pressure inside the glow discharge tube 1 by causing the pressure reducing unit 44 to reduce the pressure inside the glow discharge tube 1. At this time, in the CPU 21, the pressure in the glow discharge tube 1 decreases for the second time from the time when the pressure in the glow discharge tube 1 reaches the upper limit pressure, and the pressure in the glow discharge tube 1 decreases when the second time elapses. The pressure reducing unit 44 is controlled so as to have a pressure. In the same way, the CPU 21 repeats increasing / decreasing the pressure a specified number of repetitions.

The CPU 21 then controls the decompression unit 44 and the gas supply unit 3 to adjust the pressure in the glow discharge tube 1 to the designated final pressure. At this time, in the CPU 21, the pressure in the glow discharge tube 1 increases for the third time from the time when the pressure in the glow discharge tube 1 reaches the lower limit pressure, and the pressure becomes final when the third time elapses. The pressure reducing unit 44 and the gas supply unit 3 are controlled so as to obtain pressure.

When the pressure in the glow discharge tube 1 increases, the supplied gas pushes out the atmosphere remaining in the glow discharge tube 1, and when the pressure decreases, the extruded atmosphere is pushed out from the glow discharge tube 1. It is discharged. In this way, pumping is performed. The atmosphere is effectively discharged from the glow discharge pipe 1, and the purity of the gas supplied from the gas supply unit 3 is unlikely to decrease in the glow discharge pipe 1.

The CPU 21 then generates a glow discharge using the simulated sample 53 (S4). In S4, the CPU 21 causes the power supply unit 42 to supply a high frequency voltage to the pressing electrode 43. A glow discharge is generated between the anode 12 and the simulated sample 53, sputtering is performed on the simulated sample 53, and the inner surface of the through hole 12c of the anode 12 is coated with the constituent substances of the simulated sample 53.

Next, the CPU 21 controls the decompression unit 44 and the gas supply unit 3 to return the pressure in the glow discharge tube 1 to atmospheric pressure (S5). In S5, the CPU 21 stops the supply of gas from the gas supply unit 3. For example, the CPU 21 closes the solenoid valve 311. Further, the CPU 21 causes the decompression unit 44 to stop the decompression and allow the inside of the glow discharge tube 1 to communicate with the outside air.

The user removes the simulated sample 53 from the glow discharge tube 1, and attaches the sample 51 to be analyzed to the glow discharge tube 1 without cleaning. Next, the CPU 21 performs a process of accepting the designation of the parameter for adjusting the pressure inside the glow discharge tube 1 (S6). In S6, the CPU 21 displays the reception screen on the display unit 26 as in S1, and receives the input of the parameters on the input unit 24 by the operation of the user.

In S6, the user can arbitrarily specify parameters including the number of repetitions, the lower limit pressure, the upper limit pressure, the final pressure, the first time, the second time, and the third time, and the CPU 21 arbitrarily specifies the parameters. Accept numerically. The value of the parameter may be the same as or different from the value of the parameter received in S1. The CPU 21 stores the designated parameter in the storage unit 25. In S6, the CPU 21 may read the parameters stored in the storage unit 25 and display the reception screen including the values of the read parameters on the display unit 26. Further, the CPU 21 may display a reception screen including randomly generated parameter values on the display unit 26. The processing of S6 may be performed in advance at an earlier stage. For example, the process of S6 may be performed in parallel with the process of S1.

Next, the CPU 21 selects a gas for analysis as the gas to be supplied to the inside of the glow discharge tube 1 (S7). That is, the CPU 21 selects a gas for performing glow discharge emission analysis of the sample 51. In this embodiment, the CPU 21 selects a gas filled in the second cylinder 32 (for example, a mixed gas of argon gas and oxygen gas). The type of gas for analysis is set in advance, and setting information indicating the type of gas is stored in the storage unit 25 in advance. In S7, the control unit 2 may receive the gas designation by the input unit 24 and perform a process of selecting the designated gas.

The CPU 21 adjusts the pressure inside the glow discharge tube 1 in a state where the sample 51 is arranged so as to close the opening 13b (S8). Similar to S3, the CPU 21 controls the decompression unit 44 and the gas supply unit 3 based on the pressure value measured by the pressure sensor 45. More specifically, the CPU 21 controls the operation of the decompression unit 44, closes the solenoid valve 311 and controls the degree of opening of the solenoid valve 321 from the second cylinder 32 to the glow discharge pipe 1 through the pipe 30. Adjust the amount of inflowing gas. Similar to S3, the pressure in the glow discharge tube 1 is once reduced to the lower limit pressure, and the pressure is repeatedly increased or decreased between the lower limit pressure and the upper limit pressure by the number of repetitions. As a result, pumping is performed. The pressure in the glow discharge tube 1 is then adjusted to the final pressure.

Next, the CPU 21 performs a glow discharge emission analysis of the sample 51 (S9). In S9, the CPU 21 causes the power supply unit 42 to supply a high frequency voltage to the pressing electrode 43. A glow discharge is generated between the anode 12 and the sample 51, sputtering is performed on the sample 51, and the particles emitted from the sample 51 are excited and emit light. The light enters the spectroscopic measuring instrument 41, and the spectroscopic measuring instrument 41 disperses the incident light, measures the intensity of the light of each wavelength, and inputs the measurement result to the control unit 2. The control unit 2 receives the measurement result input from the spectroscopic measuring device 41 at the interface unit 27 and stores it in the storage unit 25. The CPU 21 performs a qualitative analysis or a quantitative analysis of the components contained in the sample 51 based on the measurement result. The processing of qualitative analysis or quantitative analysis may be performed later. The CPU 21 may display the analysis result on the display unit 26. In this way, the glow discharge emission analysis for the sample 51 is performed.

Next, the CPU 21 controls the decompression unit 44 and the gas supply unit 3 to return the pressure in the glow discharge tube 1 to atmospheric pressure (S10). In S10, for example, the CPU 21 stops the supply of gas from the gas supply unit 3 by closing the solenoid valve 321. Further, the CPU 21 causes the decompression unit 44 to stop the decompression and allow the inside of the glow discharge tube 1 to communicate with the outside air. The control unit 2 completes the process for glow discharge emission analysis.

When performing glow discharge emission analysis on a plurality of samples 51, the control unit 2 repeats the processes of S1 to S10. When the processing of S1 to S10 is performed for the second time or later, the control unit 2 may omit the processing of S1 or S6 by using the value of the parameter previously specified. Further, each time the sample 51 is changed, a different parameter value may be specified in S6.

In the present embodiment, the sample 51 and the simulated sample 53 are pressed against the glow discharge tube 1 by the pressing electrode 43, but the glow discharge emission analyzer 10 is a holder for holding the sample 51 and the simulated sample 53. It may be in the form provided with. The holder may have a function of closing the opening 13b. Further, the user may manually control the operation of the decompression unit 44 or select the gas supplied by the gas supply unit 3. Further, the glow discharge emission analyzer 10 may be in the form of using three or more kinds of gases. For example, the gas supply unit 3 may have three or more cylinders in which the filled gas is different. The control unit 2 may select different gases for each of the plurality of samples 51. Further, the gas supply unit 3 has a mechanism for mixing a plurality of gases, and the glow discharge emission analyzer 10 adjusts the type and ratio of the gases to be mixed to supply the type of gas to the glow discharge tube 1. May be in the form of changing.

The glow discharge emission analyzer 10 may include a sample exchange unit that automatically cleans the anode 12 or attaches / detaches the simulated sample 53 or the sample 51. For example, the sample exchange unit includes a mounting unit on which the simulated sample 53 and the sample 51 are placed, and a driving unit for moving the simulated sample 53 or the sample 51 mounted on the mounting unit. The driving unit moves the simulated sample 53 or the sample 51 to a position where the simulated sample 53 or the sample 51 faces the tip 12e of the cylindrical portion 12b and closes the opening 13b. The sample exchange unit is connected to the control unit 2. The drive unit automatically changes the positions of the simulated sample 53 and the sample 51 according to the control signal from the control unit 2. By using the sample exchange unit, the glow discharge emission analyzer 10 can continuously execute the glow discharge using the simulated sample 53 and the glow discharge emission analysis of the sample 51.

As described above, in the present embodiment, parameters including the number of repetitions for pressure adjustment, the lower limit pressure, the upper limit pressure, the final pressure, the first time, the second time, and the third time can be arbitrarily specified. can. Although pumping has traditionally been performed during pressure adjustment, the conditions for proper pumping are unclear. For example, appropriate pumping conditions may change depending on the structure of the glow discharge tube 1, the atmospheric condition, the type of gas supplied to the glow discharge tube 1, and the like. In the present embodiment, the pumping conditions can be adjusted by arbitrarily specifying the parameters. By designating a time different from the first time, the second time, and the third time, the time related to the increase / decrease in pressure may be specified. For example, the time corresponding to the sum of the first time and the second time, the time from when the pressure first reaches the lower limit pressure to the final pressure, or from the start of decompression until the pressure reaches the final pressure. You may specify the time.

By adjusting the pumping conditions, it becomes possible to perform pumping under appropriate conditions, and the pressure inside the glow discharge tube 1 is effectively adjusted. By performing appropriate pumping, the atmosphere is effectively discharged from the glow discharge pipe 1, and the amount of air mixed in the gas in the glow discharge pipe 1 is reduced. Therefore, the generation of glow discharge and the generation of plasma are stable, and the glow discharge emission analysis can be performed stably. In addition, it is suppressed that a component contained in the atmosphere is detected as a component of the sample 51 during the analysis, and the accuracy of the glow discharge emission analysis is improved. In addition, by performing appropriate pumping, it is possible to eliminate dark pumping. Since no dark pumping is performed, gas consumption is suppressed and the time required for adjusting the pressure is prevented from being lengthened. Therefore, the pressure in the glow discharge tube 1 is quickly adjusted. In particular, the time required to perform glow discharge emission analysis of a plurality of samples 51 is shortened.

Further, in the present embodiment, the inner surface of the through hole 12c of the anode 12 is coated with the constituent material of the simulated sample 53 by performing glow discharge using the simulated sample 53. Even if a substance such as a hydrocarbon present in the atmosphere adheres to the inner surface of the through hole 12c during cleaning, the coating makes it difficult for the adhered substance to be released. Therefore, it is unlikely that the attached substance will be detected as a component of the sample 51 by the glow discharge emission analysis. Further, since the constituent substance of the simulated sample 53 is the same as the constituent substance of the anode 12, the substance coating the inner surface of the through hole 12c does not increase the influence on the component analysis of the sample 51. Therefore, the accuracy of glow discharge emission analysis is improved.

9A and 9B are graphs showing an example of the results of glow discharge emission analysis. The horizontal axis of FIG. 9 shows the time elapsed since the sputtering of the sample 51 was started, and the vertical axis shows the emission intensity due to each element at each time point. FIG. 9A shows the result of glow discharge emission analysis by a conventional method using a silicon (Si) plate as a sample 51. In the conventional method, the inner surface of the through hole 12c of the anode 12 is not coated and pumped. FIG. 9B shows the results of glow discharge emission analysis according to the present embodiment using a Si plate as a sample 51. 9A and 9B show the emission intensity due to each element of Si, nitrogen (N), hydrogen (H), boron (B), carbon (C), oxygen (O) and argon (Ar). ing.

Among the detected elements, Si is derived from the sample 51, and Ar is derived from the gas supplied to the glow discharge tube 1. H, C and O are derived from components contained in the atmosphere. As shown in FIG. 9B, in this embodiment, the emission intensity due to H, C and O is surely reduced. That is, in the present embodiment, it is clear that the detection of components contained in the atmosphere during the analysis is reduced and the accuracy of the glow discharge emission analysis is improved.

<Embodiment 2>

FIG. 10 is a block diagram showing the configuration of the glow discharge emission analyzer 10 according to the second embodiment. The glow discharge emission analyzer 10 includes a sample plate 61 for holding the sample 51 and the simulated sample 53, and a plate holding portion 62 for holding the sample plate 61. The sample plate 61 is removable from the plate holding portion 62. The plate holding portion 62 can fix the sample plate 61. A plate driving unit 63 is connected to the plate holding unit 62. The plate driving unit 63 moves the plate holding unit 62 by a driving mechanism such as a motor. The plate driving unit 63 moves the sample plate 61 held by the plate holding unit 62 by moving the plate holding unit 62. The plate drive unit 63 can move the sample plate 61 in a direction away from the opening 13b of the glow discharge tube 1 and in a direction along the end surface 13a of the ceramic member 13. The plate drive unit 63 is connected to the control unit 2. The control unit 2 controls the operation of the plate drive unit 63.

The sample plate 61 and the plate holding portion 62 are made of a conductive member. The plate holding portion 62 is connected to the power supply portion 42. The power supply unit 42 supplies a high frequency voltage to the plate holding unit 62. By supplying the high frequency voltage to the plate holding portion 62, the high frequency voltage is also supplied to the sample plate 61. The sample plate 61, the plate holding portion 62, and the plate driving portion 63 correspond to the sample moving portion.

Further, the glow discharge emission analyzer 10 is provided with a cleaning tool 52 for cleaning the anode 12. A cleaning tool driving unit 64 is connected to the cleaning tool 52. The cleaning tool drive unit 64 moves the cleaning tool 52 by a drive mechanism such as a motor. The cleaning tool driving unit 64 can move the cleaning tool 52 in a direction away from the opening 13b of the glow discharge pipe 1. Further, the cleaning tool driving unit 64 can move the cleaning tool 52 and insert it into the through hole 12c of the anode 12. The cleaning tool drive unit 64 rotates the cleaning tool 52 in a state where the cleaning tool 52 is inserted into the through hole 12c to clean the inner surface of the through hole 12c. The cleaning tool driving unit 64 may clean the through hole 12c of the anode 12 by causing the cleaning tool 52 to perform other movements. The cleaning tool drive unit 64 is connected to the control unit 2. The control unit 2 controls the operation of the cleaning tool drive unit 64. The configuration of other parts of the glow discharge emission analyzer 10 is the same as that of the first embodiment.

FIG. 11 is a schematic perspective view showing the sample plate 61. The sample plate 61 is made of a conductive member and is formed in a rectangular flat plate shape. A plurality of sample attachment portions 611 are provided on the surface of the sample plate 61. The sample attachment portion 611 is a portion where the surface of the sample plate 61 is recessed. The simulated sample 53 adheres to one of the sample attachment portions 611, and the sample 51 adheres to the other sample attachment portion 611. The sample 51 and the simulated sample 53 are attached to the sample attachment portion 611 by a method such as placement, coating, adhesion, or crimping. The sample plate 61 holds the sample 51 and the simulated sample 53 by adhering the sample 51 and the simulated sample 53 to the sample adhering portion 611. The sample attachment portion 611 does not have to be recessed.

With the sample plate 61 holding the sample 51 and the simulated sample 53, the sample plate 61 is held by the plate holding portion 62, and the plate driving portion 63 moves the sample plate 61. The control unit 2 adjusts the position of the sample plate 61 by controlling the plate drive unit 63, and adjusts the positions of the sample 51 and the simulated sample 53 held by the sample plate 61. The control unit 2 adjusts the position of the sample plate 61 so that the sample plate 61 closes the opening 13b of the glow discharge tube 1 and the sample 51 or the simulated sample 53 faces the tip 12e of the cylindrical portion 12b of the anode 12. be able to.

FIG. 12 is a cross-sectional view showing an arrangement example of the sample plate 61 and the glow discharge tube 1 according to the second embodiment when the glow discharge is performed. When the glow discharge is performed, the sample plate 61 is arranged at a position that closes the opening 13b of the glow discharge tube 1, and the sample 51 or the simulated sample 53 is arranged at a position facing the tip 12e of the cylindrical portion 12b of the anode 12. Will be done. The sample plate 61 is arranged so that the surface of the sample plate 61 abuts on the O-ring 17. The sample 51 or the simulated sample 53 is arranged at a position facing the tip 12e of the cylindrical portion 12b. FIG. 12 shows a state in which the sample 51 faces the tip 12e of the cylindrical portion 12b. When the plate drive unit 63 pushes the sample plate 61 toward the glow discharge tube 1, the sample plate 61 is pressed against the glow discharge tube 1. The sample plate 61 may be pressed against the glow discharge tube 1 by a predetermined pressing means (not shown). By supplying a high-frequency voltage to the sample plate 61 by the power supply unit 42, a voltage is applied between the sample 51 or the simulated sample 53 held on the sample plate 61 and the anode 12.

Next, the glow discharge emission analysis method according to the second embodiment will be described. The user first holds the sample 51 and the simulated sample 53 on the sample plate 61. Specifically, the user attaches at least one sample 51 to one of the sample attachment portions 611, and attaches at least one simulated sample 53 to the other sample attachment portion 611. A plurality of samples 51 may be held on the sample plate 61. For example, a plurality of different samples 51 are attached to different sample attachment portions 611. A plurality of simulated samples 53 may be held on the sample plate 61. The user attaches the sample plate 61 holding the sample 51 and the simulated sample 53 to the plate holding portion 62.

FIG. 13 is a flowchart showing a procedure of processing according to the second embodiment executed by the control unit 2 for glow discharge emission analysis. With the sample plate 61 holding the sample 51 and the simulated sample 53 mounted on the plate holding unit 62, the CPU 21 of the control unit 2 executes the following processing according to the computer program 251. The CPU 21 performs a process of accepting the designation of the sample 51 and the simulated sample 53 used in the glow discharge emission analysis (S21). In S1, the CPU 21 displays the reception screen on the display unit 26, and the input unit 24 receives the designation of the sample 51 and the simulated sample 53 to be used by the operation of the user. For example, a number is assigned to each of the plurality of sample attachment portions 611, and the designation of the sample attachment portion 611 to which the sample 51 or the simulated sample 53 is attached is accepted. The order in which the glow discharge emission analysis is performed on the plurality of samples 51 may also be specified. The sample attachment portion 611 may be designated by any method. For example, in order to specify the order in which the analysis is performed, each sample attachment portion 611 may be specified in various orders such as horizontal, vertical, diagonal or arcuate order, skipping one, or random order. .. As a result, for example, when the sample 51 attached to one of the adjacent sample attachment portions 611 is analyzed and the sample 51 attached to the other is affected, the sample attachment portion 611 to which one sample 51 is attached is affected. By attaching the other sample 51 to the sample attachment portion 611 some distance from the sample attachment portion 611 and designating each sample attachment portion 611, the influence can be minimized. The CPU 21 stores information representing the designated contents in the RAM 22 or the storage unit 25.

Next, the CPU 21 performs a process of accepting the designation of the parameter for adjusting the pressure inside the glow discharge tube 1 (S22). In S22, the CPU 21 accepts the parameter designation as in the first embodiment. For example, the CPU 21 displays a reception screen similar to the reception screen shown in FIG. 7 on the display unit 26, and receives the input of parameters on the input unit 24 by the operation of the user. For example, parameters including the number of repetitions, lower limit pressure, upper limit pressure, final pressure, first time, second time and third time are specified. Different parameters may be specified for each of the plurality of samples 51 and the simulated sample 53, and common parameters may be specified for the plurality of samples 51 and the simulated sample 53. The CPU 21 stores information representing the specified parameter in the RAM 22 or the storage unit 25. The processing of S21 and S22 may be performed before the sample plate 61 is attached to the plate holding portion 62.

Next, the CPU 21 cleans the anode 12 (S23). FIG. 14 is a schematic view showing the positional relationship between the glow discharge tube 1, the sample plate 61, and the cleaning tool 52 according to the second embodiment at the time of cleaning. The CPU 21 arranges the sample plate 61 in the plate drive unit 63 at a position where the opening 13b of the glow discharge tube 1 is not blocked, and inserts the cleaning tool 52 into the through hole 12c of the anode 12 in the cleaning tool driving unit 64. Clean up. Cleaning removes substances adhering to the inner surface of the through hole 12c of the anode 12.

Next, the CPU 21 arranges the simulated sample 53 at a position facing the tip 12e of the cylindrical portion 12b of the anode 12 (S24). At this time, the CPU 21 separates the cleaning tool 52 from the glow discharge tube 1 and arranges the sample plate 61 at a position where the opening 13b of the glow discharge tube 1 is closed and the simulated sample 53 faces the tip 12e. .. The sample plate 61 is pressed against the glow discharge tube 1. Next, the CPU 21 selects the gas for the simulated sample 53 as the gas to be supplied to the inside of the glow discharge tube 1 (S25). In S25, the CPU 21 selects the gas as in the first embodiment. The CPU 21 then adjusts the pressure inside the glow discharge tube 1 (S26). In S26, the CPU 21 adjusts the pressure based on the pressure value measured by the pressure sensor 45 according to the designated parameters, as in the first embodiment. By adjusting the pressure, pumping is performed, the atmosphere is effectively discharged from the glow discharge pipe 1, and gas is supplied from the gas supply unit 3 to the glow discharge pipe 1.

The CPU 21 then generates a glow discharge using the simulated sample 53 (S27). FIG. 15 is a schematic view showing the positional relationship between the glow discharge tube 1, the sample plate 61, and the cleaning tool 52 according to the second embodiment when performing glow discharge using the simulated sample 53. The cleaning tool 52 is arranged at a position separated from the glow discharge pipe 1. The sample plate 61 closes the opening 13b of the glow discharge tube 1, and the simulated sample 53 held by the sample plate 61 faces the anode 12. The CPU 21 causes the power supply unit 42 to supply a high frequency voltage to the plate holding unit 62. A glow discharge occurs between the anode 12 and the simulated sample 53. Sputtering is performed on the simulated sample 53, and the inner surface of the through hole 12c of the anode 12 is coated with the constituent material of the simulated sample 53.

Next, the CPU 21 controls the decompression unit 44 and the gas supply unit 3 to return the pressure in the glow discharge tube 1 to atmospheric pressure (S28). Next, the CPU 21 arranges the sample 51 at a position facing the tip 12e of the cylindrical portion 12b of the anode 12 (S29). At this time, the CPU 21 removes the simulated sample 53 from the position facing the tip 12e by moving the sample plate 61. Further, the CPU 21 adjusts the position of the sample plate 61 so that the sample plate 61 closes the opening 13b and the sample 51 faces the tip 12e. The sample plate 61 is pressed against the glow discharge tube 1.

Next, the CPU 21 selects a gas for analysis as the gas to be supplied to the inside of the glow discharge tube 1 (S30). In S30, the CPU 21 selects the gas as in the first embodiment. The CPU 21 then adjusts the pressure inside the glow discharge tube 1 (S26). Similar to the first embodiment, the CPU 21 adjusts the pressure based on the pressure value measured by the pressure sensor 45 according to the designated parameters. Pumping is performed by adjusting the pressure, and then the pressure in the glow discharge tube 1 is adjusted to the final pressure.

Next, the CPU 21 performs a glow discharge emission analysis of the sample 51 (S32). FIG. 16 is a schematic view showing the positional relationship between the glow discharge tube 1, the sample plate 61, and the cleaning tool 52 according to the second embodiment when performing glow discharge emission analysis. The cleaning tool 52 is arranged at a position separated from the glow discharge pipe 1. The sample plate 61 is arranged at a position different from that in the case of performing glow discharge using the simulated sample 53, and the sample 51 held by the sample plate 61 faces the anode 12. In S32, the CPU 21 causes the power supply unit 42 to supply a high frequency voltage to the plate holding unit 62. A glow discharge is generated between the anode 12 and the sample 51, sputtering is performed on the sample 51, and the particles emitted from the sample 51 are excited and emit light. The spectroscopic measuring instrument 41 disperses the incident light, measures the intensity of the light of each wavelength, and inputs the measurement result to the control unit 2. The control unit 2 stores the measurement result in the storage unit 25. The CPU 21 performs a qualitative analysis or a quantitative analysis of the components contained in the sample 51 based on the measurement result. In this way, the glow discharge emission analysis for the sample 51 is performed.

Next, the CPU 21 controls the decompression unit 44 and the gas supply unit 3 to return the pressure in the glow discharge tube 1 to atmospheric pressure (S33). Next, the CPU 21 determines whether or not to end the process for glow discharge emission analysis (S34). For example, the CPU 21 determines that the process is completed when the glow discharge emission analysis is performed on all the samples 51 held on the sample plate 61. For example, the CPU 21 determines that the process is not completed when the sample 51 for which the glow discharge emission analysis has not yet been performed remains. The CPU 21 may receive an instruction as to whether or not to end the process by the operation of the user at the input unit 24, and make a determination according to the received instruction. If it is determined that the process is not completed (S34: NO), the CPU 21 returns the process to S23. When the sample plate 61 holds a plurality of samples 51, the processes of S23 to S34 are repeated, and glow discharge emission analysis is performed for each sample 51. If it is determined to end the process (S34: YES), the CPU 21 ends the process for glow discharge emission analysis.

As described above, also in the second embodiment, by adjusting the pumping conditions when performing the glow discharge emission analysis, it is possible to perform pumping under appropriate conditions, and the glow discharge tube 1 is effectively contained. Pressure adjustment is performed. Further, by performing glow discharge using the simulated sample 53, glow discharge emission analysis is performed with the inner surface of the through hole 12c of the anode 12 coated. Glow discharge emission analysis can be performed stably, and the accuracy of glow discharge emission analysis is improved. Further, in the second embodiment, the sample plate 61, the plate holding unit 62, and the plate driving unit 63 automatically arrange and remove the simulated sample 53 and arrange the sample 51. When performing glow discharge emission analysis of a plurality of samples 51, the plurality of samples 51 are sequentially arranged. The amount of work done by the user is reduced, and glow discharge emission analysis is performed quickly. In particular, the time required to perform glow discharge emission analysis of a plurality of samples 51 is shortened.

In the second embodiment, an example in which the parameters for pressure adjustment are collectively specified is shown, but the glow discharge emission analyzer 10 determines the parameters one by one when performing the glow discharge emission analysis for each sample 51. The designation may be accepted. Further, in the second embodiment, the sample moving portion is composed of the rectangular flat plate-shaped sample plate 61, the plate holding portion 62, and the plate driving portion 63, but the sample moving portion may have other configurations. good. For example, the shape of the sample plate 61 may be a shape other than a rectangular flat plate such as a disk. For example, the sample moving unit may include a sample holding unit that holds the sample 51 and the simulated sample 53, and a driving unit that drives the sample holding unit to move the sample 51 and the simulated sample 53. The sample moving unit may have a form including a turntable on which the sample 51 and the simulated sample 53 are placed. The sample moving portion may be in a form of holding the sample 51 and the simulated sample 53 by a method other than adhesion such as grasping.

The present invention is not limited to the contents of the above-described embodiment, and various modifications can be made within the scope of the claims. That is, an embodiment obtained by combining technical means appropriately modified within the scope of the claims is also included in the technical scope of the present invention.

1 Glow discharge tube 10 Glow discharge emission analyzer 12 Anode (electrode)
12c Through hole 13b Opening 2 Control unit 21 CPU
24 Input unit 25 Storage unit 26 Display unit 3 Gas supply unit 41 Spectroscopic measuring instrument 42 Power supply unit 43 Pressing electrode 44 Decompression unit 51 Sample 52 Cleaning tool 53 Simulated sample 61 Sample plate 62 Plate holding unit 63 Plate drive unit

Claims (8)

In a glow discharge emission analysis method using a glow discharge emission analyzer including a glow discharge tube, a decompression unit for reducing the pressure inside the glow discharge tube, and a gas supply unit for supplying gas to the inside of the glow discharge tube.
Arbitrarily specify the upper limit pressure, lower limit pressure, and final pressure,
By controlling the decompression unit and the gas supply unit, the inside of the glow discharge pipe is depressurized, and the pressure inside the glow discharge pipe is increased or decreased between the designated upper limit pressure and the lower limit pressure.
After that, the pressure inside the glow discharge tube is adjusted to the designated final pressure.
A glow discharge emission analysis method, characterized in that a glow discharge is generated after adjusting the pressure inside the glow discharge tube to the final pressure. The number of times to increase or decrease the pressure inside the glow discharge tube is arbitrarily specified.
The glow discharge emission analysis method according to claim 1, wherein the pressure inside the glow discharge tube is repeatedly increased or decreased a specified number of times. The first time to be applied to increase the pressure inside the glow discharge tube from the lower limit pressure to the upper limit pressure, and to reduce the pressure inside the glow discharge tube from the upper limit pressure to the lower limit pressure. Arbitrarily specify the second time to be
The pressure inside the glow discharge tube is reduced to the lower limit pressure.
During the designated first hour, the pressure inside the glow discharge tube is increased.
The glow discharge emission analysis method according to claim 1 or 2, wherein the pressure inside the glow discharge tube is reduced during a designated second time. The glow discharge tube has an electrode and
A glow discharge is generated between the electrode and the simulated sample in a state where the simulated sample having the same components as the electrode is arranged so as to face the electrode.
Remove the simulated sample,
Place the sample so that it faces the electrode.
The glow discharge emission analysis method according to any one of claims 1 to 3, wherein a glow discharge is generated between the electrode and the sample to perform glow discharge emission analysis. Using the simulated sample and the sample moving unit that holds and moves the simulated sample and the sample.
The sample moving unit arranges the simulated sample at a position facing the electrode.
After generating a glow discharge between the electrode and the simulated sample, the simulated sample is removed from the position by the sample moving unit, and the sample is placed at a position facing the electrode. The glow discharge emission analysis method according to claim 4. The type of gas supplied to the inside of the glow discharge tube by the gas supply unit is changed depending on whether the simulated sample is arranged to face the electrode or the sample is arranged to face the electrode. The glow discharge emission analysis method according to claim 4 or 5, wherein the glow discharge emission analysis method is characterized. In a glow discharge emission analyzer including a glow discharge tube, a decompression unit for reducing the pressure inside the glow discharge tube, a gas supply unit for supplying gas to the inside of the glow discharge tube, and a control unit.
The control unit
The upper limit pressure, lower limit pressure, and final pressure can be specified with arbitrary values.
By controlling the decompression unit and the gas supply unit, the pressure inside the glow discharge tube is increased or decreased between the designated upper limit pressure and the lower limit pressure, and then the pressure inside the glow discharge tube is designated. Adjust to the final pressure,
A glow discharge emission analyzer characterized in that a glow discharge is generated after adjusting the pressure inside the glow discharge tube to the final pressure. The glow discharge tube has an electrode and
A sample moving unit for holding the simulated sample and the sample having the same components as the electrode and moving the held simulated sample and the sample is further provided.
The sample moving unit arranges the simulated sample at a position facing the electrode, and arranges the simulated sample at a position facing the electrode.
The control unit generates a glow discharge between the electrode and the simulated sample in a state where the simulated sample is arranged at the position.
In the sample moving unit, the simulated sample is removed from the position, and the sample is placed at a position facing the electrode.
The glow discharge according to claim 7, wherein the control unit generates a glow discharge between the electrode and the sample in a state where the sample is arranged at the position, and performs a glow discharge emission analysis. Luminescent analyzer.

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